Polymercapto condensation polymers derived from maleic anhydride copolymers and aminothiols and their application for cosmetic purposes



United States Patent 3,472,820 POLYMERCAPTO CONDENSATION POLYMERS DERIVED FROM MALEIC ANHYDRIDE CO- POLYMERS AND AMINOTHIOLS AND THEIR APPLICATION FOR COSMETIC PURPOSES Grgoire Kalopissis, Paris, Charles Zviak, Franconville,

and Andr Viout, Paris, France, assignors to Socit anonyme dite: LOreal i I No Drawing. Filed June 14, 1965, Ser. No. 463,953 Claims priority, application France,.June 19, 1964,

978,832; Jan. 18, 1965, 2,339 Int Cl. C08f 15/14, 27/06; A61k 7/10 US. Cl. 260-78.5 14 Claims ABSTRACT OF THE DISCLOSURE OCOCH COOCH and C=N,

Q is a radical having the following formula:

Il a R2 N(EH-(CHzh-[NH-C 0E(CHi)pl4'-sr 1 in which:

R, is selected from the group consisting of H and CH R is selected from the group consisting of H and COOH, q is a whole number between 1 and 5, inclusive, q is an integer from 0 to l inclusive, p is an integer from 0 to 1 inclusive, Q is a radical having the formula:

R is selected from the group and lower alkyl, R, is selected from the group consisting of a lower alkyl and a radical having the formula consisting of hydrogen,

in which is selected from the group consisting of lower alkyl amines and a heterocyclic ring, m is a whole number lying between 2 and 4, inclusive.

ice

It is also well known that hair set in this manner retains the desired form only for a relatively short time, and that it is extremely-sensitive to humidity, since absorption of water by the hair results in destruction of the set.

Attempts have been made to overcome this disadvantage by applying to the hair aqueous or water-alcohol solutions of natural or synthetic macromolecules which, after the solvent has evaporated, form a film on the hair.

The essential object of these films is to protect the hair against humidity, but it is also necessary for them to improve, if possible, the sheen, flexibility and manageability of the hair. It is also essential that these films be easily removed from the hair by washing or brushing, without powdering, i.e. without having the film disintegrate into a. multitude of fine particles.

The compositions heretofore utilized for this purpose include vegetable resins, alginates, cellulosic derivatives,

Ipolyvinylpyrrolidone, vinyl-pyrrolidone/vinyl acetate copolymers, and vinyl acetate/ethylenic acid copolymers.

All of the compositions heretofore used have inherent disadvantages.

To begin with, they have an insufficient afnnity for keratin and do not adhere well to the hair, so that they come off easily when the hair is being combed or brushed, so that such brushing results in the rapid elimination of the wave resulting from the set.

Moreover, the film is usually hygroscopic, so that the sheen of the hair deteriorates rapidly.

Applicants assignee has already suggested the use of polymercapto polymers. (See French Patent No. 1,349,- of Mar. 28, 1962.) These exhibit a notable afiinity for keratinic fibers and have cosmetic applications of substantial importance. However, the use of these polymers to set the hair does not produce entirely satisfactory results in that the resulting film on the hair has a crystalline character which leads to powdering and leaves the hair dull.

After long research, applicants have discovered new polymers which may be very advantageously used in setting the hair and which at least partially avoid the aforesaid disadvantages, since, on the one hand, they adhere well to the hair and form almost humidity-proof films, and on the other hand, they impart an especially soft and bright appearance to the hair, while rendering it easy to put up.

An object of the present invention is to provide a new article of manufacture which consists of a polymer having SH groups, alkyl groups and amino alkyl groups in its molecule, characterized by the fact that it has the following formula:

R and R", which may or may not be identical, are selected from the group consisting of a hydrogen atom, a lower alkyl radical, a phenyl radical, and a lower alkoxy radical; I

R' may be a hydrogen atom, the OCOCH radical, the

COOCH radical, or the CEN radical;

.n is awhole number;

Q is a radical having the following formula:

N-CH-(CH -[NH-CO-CH-(CHzhk -SH in which:

R represents H or CH R represents H or COOH q is a whole number between 1 and 5, inclusive; q is equal to zero or 1,

p is equal either to zero or 1,

Q is a radical having the following formula:

in which:

R is a hydrogen atom or a lower alkyl; R, is a lower alkyl, a radical having the formula in which r and r are identical or difierent lower alkyls, or may form part of a heterocycle such as that of morpholine or piperidine; and

m is a whole number equal to 2, 3 or 4.

The proportions of the substituents Q and Q of Formula I may be varied within broad limits, for example from 1 to 99% and preferably from 20 to 80% of the thiols.

Another object of the present invention is to provide new polymers having the above-mentioned Formula I, which are characterized by the fact that R' and R" each represent a hydrogen atom, while R' represents either the --OCOCH the C=N radical, or the -COOCH radical.

A further object of the invention is to provide the new polymer having the above Formula I, in which R is a hydrogen atom, R" is the CH radical, and R is the -COOCH radical.

In a preferred embodiment of the invention the polymercapto condensation polymers hereinbefore defined have a value of n such that they are soluble in water, at least in an alkaline medium.

Another object of the present invention is to provide a process for manufacturing the aforesaid polymers, which process consists, on the one hand, in condensing aminothiols or amino mercapto-amines having the following formula:

in which R R q, p, and q have the same values already given, and, on the other hand, condensing alkyl amines having the formula:

NH-( CHflm-CHr-CHl-RA in which R R and m have the values hereinbefore assigned thereto on a copolymer having the formula:

in which R, R" and R' have the values hereinbefore indicated.

Among the compositions which may be substituted as Q in Formula II are B-mercaptoethylamine, cysteine, N- monomethyl mercaptoethylamine, and N,( 8-aminoethyl) thioglycolamide, but this list is not exhaustive.

Among the compositions which may be substituted as Q in Formula III are butylamine, N,N-diethyl-propylenediarnine and N-(B-amino-ethyl) morpholine, but this list is not exhaustive.

The new polymers corresponding to Formula I may be easily prepared by reacting with polymers corresponding to Formula VI a mixture in the proportions previously specified of aminothiols or amido mercaptoamines according to Formula IV and amines according to Formula V. The reaction is carried out in an aqueous medium at room temperature. The desired product is then isolated by precipitation in an acid medium.

During the condensation it is desirable to add a ase to neutralize the carboxylic function which forms and permit the dissolution of the polymers formed.

It should be noted that the plastic properties of the films formed by the polymers depend to a certain extent on the nature of the base which is used to neutralize the carboxylic function.

The new polymers which have just been described are particularly valuable for use for cosmetic purposes.

In particular, they may be used to prepare compositions for setting" the hair which form transparent, lustrous, colorless, flexible films.

Moreover, as a consequence of the presence of the mercapto groups, these polymers have an excellent affinity for the hair.

In accordance with the invention, it is possible to vary the resistance of these films to humidity as desired by varying the proportions of the substituents Q and Q' in the copolymers. The resistance to humidity increases with any increase in the proportion of the substituent Q.

The resinous polymers of this invention may be used as.setting compositions, either in the form of lotions containing a low percentage of polymers, or in the form of. gels having a high percentage of polymers. These compositions make it possible to make hair sets last considerably longer, while rendering the hair easy to manage, soft in appearance, lustrous and silky.

Depending on the objective sought, the polymers of this invention may be used alone or mixed with other cosmetic agents, e.g., plasticizers such as glycol ethers, cationic surfactants such as quaternary ammoniums, swelling agents such as urea, perfumes, sequestrants, pigments, etc.

Of course, several of the resinous polymers of this invention may be used as a mixture with each other, or they may be used in mixtures containing other known resins, previously used in cosmetic compositions.

When they are used for setting the hair, the polymers of this invention may be advantageously dissolved in aqueous alcoholic solutions of between 20 and 50 degrees and at concentrations preferably of the order of 2 to 3%, but which may rise to 10% or higher.

It is also preferable to neutralize the carboxylic function present with a base such as one of the amino alcohols, which are particularly suitable for this purpose.

It is also noteworthy that when polymers of this invention are used to impregnate keratinic textile fibers such as wool, these fibers may be effectively dyed with reactive dyes.

In order that the invention may be clearly understood several examples will now be described purely by way of example, without limiting the scope of the invention to the details thereof.

Example 1.Condensation of B-mercapto ethylamine and N,N-diethylpropylene diamine on an ethylene/maleic anhydride copolymer The copolymer having the following repeating formula is prepared:

37.8 g. (A mol.) of the hydrochloride of p-mercapto ethylamine, 86.6 g. /3 mol.) of N,N-diethylpropylene diamine and 600 cc. of water is placed in a receiver provided with an agitator, a thermometer, a tube for supplying nitrogen, and dropping funnel.

13.3 g. (Va mol.) of NaOH is then added to liberate the amine. Then, while stirring and cooling the solution, 71.5 g. (0.5 mol.) of the ethylene/maleic anhydride copolymer sold by the Monsanto Chemical Co. as D.X. 840-11 is then added, the ratio of ethylene to maleic anhydride being 1:088. The specific viscosity of the copolymer at 25 C., has been brought to 0.1 at a concentration of 1% when in solution in dimethylformamide.

After having introduced the polymer into the receiver, 20 g. (0.5 mol.) of NaO I-I is added to the reaction mixture in small tablets. Then 71.5 g. of the ethylene/maleic anhydride copolymer is added, followed by 20 g. of NaOH tablets in small portions.

At the end of 3 or 4 hours the reaction is terminated and the desired product is isolated by acidification, salted out by means of sodium chloride.

This yields 235 g. of the desired copolymer which appears in the form of a powder which is soluble in water at a neutral or alkaline pH. This represents a yield of about 80 to 85%.

It should be noted that in the final product the tertiary amine function is present in the form of the hydrochloride and that the product contains about 12.5% of sodium chloride, as determined by an analysis of the chloride ion content.

The product is then purified by dissolving it in a mixture of dimethyl formamide and alcohol, the insoluble sodium chloride being eliminated by filtration. The desired product is precipitated from the filtrant by adding ether.

The following analyses have been made:

(a) Of the unpurified product--Calculated: Cl-, 8.45% (theoretical hydrochloride content); SH, 3.34% (taking into account the sodium chloride present). Found: C11 16%; SH, free.2.7%; total 3.3%.

(b) Of the purified product-Calculated: Cl, 8.45 SH, 3.78% (taking into account the sodium chloride present). Found: Cl, 9.15% (there was a 1.15% residue of sodium chloride); SH, free 2.10%; total 2.76%.

The expression Total --SH is used to indicate the sum of the free SH groups in the product and the SH groups which could be separated from the oxidized (-SS-) portion of the product by total reduction during the analysis.

Example 2.Condensation of crysteine and the N,N-diethylpropylene diamine on an ethylene/maleic anhydride copolymer This is eifectuated under the same conditions as those described in Example 1, except that an equivalent quantity of crysteine is substituted for the B-mercapto ethylamine. This yields 47% by weight of a gum which, after purification by dissolving it in dimethyl formamide and precipitation with ether, appears in the form of a pulverulent mass which is soluble in water at a neutral or alkaline pH.

The resulting product was analyzed, with the following results:

Calculated: Cl", 8.05%; SH, 3.62%. Found: Cl, 7.6%; SH, free 1.68%; total 2.96%.

Example 3.Condensation of N-(/3-aminoethyl)thioglycolamide and N,N-diethylpropylene diamine on an ethylene/maleic anhydride copolymer This process is carried out under the same conditions as those described in connection with Example 1, except that the fl-mercapto ethylamine is replaced by an equivalent quantity of N- (B-arninoethyl)thioglycolamide.

After vacuum drying the process yields about 80% by weight of the desired product in the form of a powder soluble in water at a neutral or alkaline pH.

The following analysis of the end product was made:

Calculated: Cl-, 7.93%; SH, 3.13% (taking into account the sodium chloride). Found: Cl, 15% (which 6 corresponds to 11.7% sodium chloride); SH, free 2.45%; total 2.6%.

The product thus obtained may be purified by dissolving it in dimethyl formamide and precipitating it with ether.

N-(,Q-aminoethyl)thioglycolamide having the formula:

'has been obtained in the following manner:

64 g. (1 mol.) of 96% ethylenediamine is placed in a recipient provided with an agitator, a reflux cooling column, a thermometer, a dropping funnel and a tube for supplying nitrogen. 126 g. (1 mol.) of a 95% solution of ethyl thioglycolate in 100 cc. of absolute alcohol is then introduced drop by drop, while constantly stirring and maintaining the temperature at about 4045 C.

When this addition has been completed the solution is heated under reflux for 2-0 minutes.

The product precipitates on cooling. After draining and drying 107 g. of N-(B-aminoethyl)thioglycolamide is obtained, representing a yield of about The substance thus obtained is in the form of a white crystalline powder, 99% pure, having a melting point of 133 C.

Example 4.Condensation of B-mercapto ethylamine and butylamine on an ethylene/maleic anhydride copolymer This condensation yields about 89% by weight when carried out as described in the foregoing examples, except that the N,N-diethyl-ethylene diamine is replaced by a corresponding quantity of butylamine.

After precipitation in an acid medium, the product is washed with water and, when dried, is a powder soluble in water in an alkaline medium. 7

It should be noted that, in the present case, the isolated composition is not contaminated with sodium chloride, so that further purification is unnecessary.

The composition obtained has been analyzed as follows:

Calculated: SH, 4.9%. Found: SH, free 3.6%; total 4.9%.

Example 5 .Condensation of fl-mercapto ethylamine and N-(fl-aminoethyl)morpholine on an ethylene/maleic anhydride copolymer The condensation is carried out with a yield of about 65% by proceeding as described in Example 1, except that the N,N-diethyl-ethylene diamine is replaced by an equivalent quantity of N-(fl-aminoethyDmorpholine.

The product obtained is in the form of a powder which is soluble in water at a neutral or alkaline pH. The powder was analyzed with the following results:

Calculated: Cl, 8.7%; Total SH, 3.92%; Free SH, 3.92%. Found: CI, 11.7 (ClNa, 4.8%); Total -SH, 3.85%; Free SH, 2.35%.

Example 6.-Condensation of N-(p-aminoethyDthioglycolamide and butylamine on an ethylene/maleic anhydride copolymer The condensation is carried out with a yield of about by proceeding as described in Example 3, except that the N,N-diethyl-propylene diamine is replaced by an equivalent quantity of butylamine.

The product thus obtained is soluble in water in an alkaline medium, and was analyzed with the following results:

Calculated: Total --SH, 4.65%; Free SH, 4.65%. Found: Total SH, 4.55%; Free SH, 2.52%.

Example 7.Condensation of fi-mercaptoethylamine and N,N-diethyl-propylenediamine on an ethylene/maleic anhydride copolymer The desired product is obtained with a yield of about 82% by weight by following the same procedure as in Example 1, except that the quantities of amino-thiol and diamine are altered so that each is equal to 0.5 mol. for a total of 1 mol. of ethylene/maleic anhydride copolymer. After drying the product obtained is a powder which is soluble in water at a neutral or alkaline pH. This powder has been analyzed with the following results:

Calculated: SH, 6.28%. Found: SI-l, free 4.9%; total 5.5%.

Example 8.--Condensation of B-mercapto ethylarnine and N,N-diethyl-propylenediamine on an ethylene/maleic anhydride copolymer The process is the same as that of Example 1, except that of a mol. of Si-mercapto ethylarnine hydrochloride is used for each mol. of N,N-diethylpropylene diamine.

The product is purified by dissolving it in dimethyl formamide and precipitating it with ether. The composition is obtained in the form of the hydrochloride, with a yield of about 50% by weight. It is soluble in water at a neutral or alkaline pH. The following analysis was made:

Calculated: Cl+, 9.7% SH, 2.2%. Found: Cl, 8.2%; SH, free 1.22%; total 1.76%.

Example 9.-Condensation of B-rnercapto ethylarnine and butylamine on a styrene/maleic anhydride copolymer The copolymer having the following repeating formula is prepared:

COOH =0 C OOH /=O NH 1 TH CH1 34110 in the same manner as in Example 1, but utilizing: instead of the ethylene/maleic anhydride copolymer an equivalent quantity of the styrene/maleic anhydride copolymer sold under the tradename Resin SMA 1000 A by the Texas Butadiene Chemical Corp., and in which the styrene/ maleic anhydride ratio is 1:0.86; and instead of N,N-diethyl-propylenediamine, an equivalent quantity of butylamine.

The desired product is isolated in a conventional manner by precipitation in an acid medium. A yield of 93% is obtained and the product is in the form of a powder, an analysis of which gave the following results:

Calculated: Free SH, 3.88%; Total -SH, 3.88%; N, 4.53%. Found: Free SH, 1.1%; total --SH, 3.16%; N, 3.95%.

Example 10.Condensation of fi-mercapto-ethyl-amine and n-butyl-amine on a vinyl acetate/maleic anhydride copolymer A polymercapto condensation copolymer having the following repeating formula is prepared:

by condensing fi-mercapto-ethyl-amine and n-butyl-amine on a vinyl alcetate/maleic anhydride copolymer, in the following manner:

The starting copolymer is a vinyl acetate/maleic anhydride copolymer obtained in a conventional manner by copolymerizing equimolecular quantities of vinyl acetate and maleic anhydride in toluene in the presence of benzoyl peroxide, which acts as a catalyst.

This copolymer, in a 1% solution in dimethyl formamide, has a specific viscosity of 0.17 at a temperature of 25 C.

The anhydride function has been introduced in a proportion such that the molar ratio between the vinyl acetate and maleic anhydride in this polymer is 0.93/1.

The copolymerization has been so carried out as to produce a copolymer which is water-soluble in a basic medium.

3.89 (0.033 mol.) of the hydrochloride of B-mercaptoethyl-amine, 4.9 grams (0.066 mol.) of n-butylamine and cm. of water are placed in a vessel provided with an agitator, a thermometer, a tube for introducing nitrogen, and a dropping funnel.

The amine is then liberated from its hydrochloride by adding 3.3 cm. (0.033 mol.) of an aqueous 40% soda solution.

8.9 grams (0.5 mol.) of the vinyl acetate/maleic anhydride copolymer is then added, while stirring and cooling the solution.

5 cm. (0.5 mol.) of an aqueous 40% sodium hydroxide solution is then added to liberate the amine and solidify the carboxyl group of the copolymer.

8.9 grams (0.5 mol.) of the vinyl acetate/maleic anhydride copolymer is then added, together with 5 cm. (0.5 mol.) of an aqueous 40% sodium hydroxide solution.

The reaction is completed in three hours.

The solution is then acidified with hydrochloric acid to precipitate the desired product, which yields 78% by weight, i.e. 19.5 grams of the copolymer according to the invention.

The product is yielded in the form of a white powder which is water soluble at an alkaline pH, and which has the following analysis:

Percent SH calculated 5.24 SH found 2.7

After reducing the oxidized form of the products, a new analysis was made, with the following results:

Percent SH calculated 5.24 SH found 5.3

Example 11.Condensation of fl-mercapto-ethyl-amine and N,N-diethyl-propylene-diamine on a methyl methacrylate/maleic anhydride copolymer In accordance with the invention a poly mercapto condensation polymer having the following repeating formula is prepared:

by condensing fl-mercapto-ethyl-amine and N,N-diethylpropylenediamine on a methyl methacrylate/maleic anhydride copolymer, in the following manner:

The starting polymer is a methyl methacrylate/maleic anhydride copolymer obtained in a conventional manner by copolymerizing equimolecular quantities of methyl methacrylate and maleic anhydride in toluene in the presence of azo-bis-iso-butyronitrile, which acts as a catalyst.

A 1% solution of this polymer in dimethyl-formamide has a specific viscosity of 0.088 at a temperature of 25 C.

The molar ratio between the methyl methacrylate and the maleic anhydride in this polymer is determined by measurement of the anhydride function as equal to 1.52/1.

Under the same conditions as in Example lfl-mercaptoethyl amine and N,N-diethyl-propylene-diamine are condensed on the methyl methacrylate/maleic anhydride copolymer which has been obtained in the manner already described, using 0.5 mol. of aminothiol and 0.5 mol. of diamine per mol. of methyl methacrylate/maleic anhydride copolymer.

After precipitation and purification, a yield of 68% by weight of the desired copolymer is obtained in the form of a white powder which is water soluble at a neutral or alkaline pH.

This powder has been analyzed as follows:

Percent SH calculated 4.45 SH found 2.71

After the oxidized form of the product has been reduced, a new analysis yielded the following results:

Percent SH calculated 4.45 SH found 3.80

Example 12.Condensation of N-(fi-amino-ethyDthioglycolamide and n-butylamine on an acrylonitrile/ maleic anhydride copolymer In accordance with the invention a polymercapto condensation polymer having the following repeating formula is prepared:

by condensing N-(B-amino-ethyl)thioglycolamide and nbutylamine on an acrylonitrile/maleic anhydride copolymer, in the following manner.

An acrylonitrile/maleic anhydride copolymer is used as the starting copolymer. This is obtained by copolymerizing equimolecular quantities of acrylonitrile and maleic anhydride in toluene in the presence of benzoyl peroxide, which acts as a catalyst.

The copolymer obtained, when in a 1% solution in dimethyl formamide, has a specific viscosity of 0.055 at a temperature 25 C.

The molar ratio between the acrylonitrile and the maleic anhydride, is determined by measuring the amine function as equal to 1.19/ 1.

The method is the same as that of Example 10, with the condensation of diamine and aminothiol on this copolymer, except that the B-mercapto-ethyl-amine is re placed by a molecularly equivalent quantity of N-(flaminoethyl)thioglycolamide, and the vinyl acetate is replaced by acrylonitrile.

' After the resulting product has been precipitated by means of hydrochloric acid, it is dried, and a yield of 47% by weight of the desired product is obtained.

The product is in the form of a white powder which is water-soluble at an alkaline pH, and has been analyzed with the following results:

Percent SH calculated 4.34 SH found 2.6

After reduction of the oxidized'form of the product, a new analysis yielded the following results:

Percent SH calculated 4 34 SH found 3.5

A polymercapto condensation polymer having the following repeating formula is prepared:

CH2CH CH'lCHCH2CH-CHCH COOCH: lOOH GO COOCHaCOOH CO NH IIIIH CH2 CH2 I Hg (3H1 SH (H51 CrHt C2115 by condensing fl-mercapto ethylamine and N,N-diethylpropylene-diamine on a methyl acrylate/maleic anhydride copolymer obtained in a conventional manner by copolymerizing equimolecular quantities of methyl acrylate and maleic anhydride in toluene in the presence of benzoyl peroxide, which acts as a catalyzer.

This copolymer, as a 1% solution in dimethyl-formamide has a specific viscosity of 0.093 at a temperature of 25 C.

The molar ratio between the methyl acrylate and maleic anhydride has been determined by measurement of the anhydride function to be equal to 0.9/ 1.

By treating the copolymer obtained in this manner in the same way as that described in Example 11, a yield amounting to 70% by weight of a white precipitate is obtained. This precipitate, when dried, apears in the form of a powder which is water-soluble at a neutral or alkaline pH. An analysis of this powder yielded the following results:

Percent SH calculated 5.25 SH found u.. 3.54

After reducing the oxidized form of the product, a new analysis gave the following results:

Percent SH calculated 5 .25

SH found 4.27

Example 14 Process for producing a hair-setting lotion having following composition:

the

Water, q.s.p. cc

The resin is first dissolved in 60 cc. of water in the presence of 2-amino-2-methyl-l-propanol until the pH reaches 8.2. The tetrasodium salt of ethylene diamine tetracetic acid is then added to serve as a sequestrant for metals, followed by the mixture of ethyl alcohol and perfume. The volume is then increased to 100 cc. by adding distilled water and, to a pH of 8.5, by adding 2-amino-2-methyl-1- propanol.

20 cc. of this solution is then applied to hair which has been washed and dried, taking care to distribute the solution uniformly over the hair. The hair is then set in a conventional manner. Hair which has been thus treated is lustrous, soft, silky and easily arranged.

The lotion which has just been described materially prolongs the life of the set while keeping the air in shape without maning it dull, even in very humid weather.

1 1 EXAMPLE 1s A setting lotion having the following composition is prepared:

The condensation product of the ethylene/maleic an- The procedure is the same as that of Example 14. The results obtained are excellent.

Example 16 A setting lotion having the following composition is prepared:

The condensation product of the ethylene/maleic anhydride copolymer with fl-mercaptoethylamine and butylamine, obtained as in Example 4 g 2.5 Ethyl alcohol, q.s.p. degrees 50 Triethanolamine, q.s.p. pH 7 Tetrasodium salt of ethylene diamine tetracetic acid g 0.1 Water, q.s.p. cc 100 Example 17 A setting lotion having the following composition is prepared in the same manner as described in connection with Example 16:

Resin resulting from the condensation of fi-rnercaptoethylamine and N,N-diethylpropylenediamine on the ethylene/maleic anhydride copolymer, obtained as in Example 1 g 2.5 Tetrasodium salt of ethylene diamine tetracetic acid g 0.1 N,N-dimethyl ethanolamine, q.s.p. pH 8 Ethyl alcohol, q.s.p. degrees 25 Water, q.s.p. cc 100 The application of this lotion to the hair yields excellent results.

Example 18 A setting lotion having the following composition is prepared in the same manner as described in connection with Example 14.

Condensation product of ethylene/maleic anhydride copolymer with fl-mercaptoethylamine and N,N- diethyl-propylenediamine, obtained as in Example 7 Vinyl pyrrolidone/vinyl acetate copolymer g 1 Ethyl alcohol, q.s.p. degrees 35 2-amino-2-methyl-l-propanol, q.s.p pH 9 Perfume g 0.2

Water, q.s.p. cc 100 This lotion also gives very satisfactory results.

1 2 Example 19 An aerosol bomb containing the following ingredients is used to provide an aerosol foam for setting the hair: Condensation product of ethylene/maleic anhydride copolymer with cysteine and N,N-diethyl-propylene diamine, obtained as in Example 2 g.. Ethyl alcohol, q.s.p degrees 25 2-amino-2-methyl-l-propanol, q.s.p. pH 8.5

Emulsifying agent (cetyl-stearyl alcohol condensed with mols. of ethylene oxide) g 2 Perfume g 0.2 Water, q.s.p. g 93 Propellant g 7 The aerosol bomb is made by first solubilizing the resin in 30 cc. of water in the presence of 2-amino-2- methyl-l-propanol. Cetyl-stearyl alcohol (which has first been dissolved in 20 cc. of water, while being slightly heated) is then added, after which the mixture of ethyl alcohol and perfume is added.

The pH is then adjusted to 8.5 by adding the necessary quantity of 2-amino-2-methyl-l-propanol and the weight increased to 93 g. by adding distilled water.

The bomb is completed by adding 7 g. of a conventional propellant such as the fluorinated hydrocarbon sold as Freon 12.

The product is applied in the form of a very transient foam, which facilitates its uniform distribution throughout the hair, which has previously been washed and dried.

The hair is then set in the usual manner, with excellent results.

Example 20 10 g 3 Ethyl alcohol, q.s.p degrees 25 2-amino-2-methyl-l-propanol, q.s.p. pH 8.5

Tetrasodium salt of ethylene diamine tetracetic acid g 0.1 Perfume g 0.2 Water, q.s.p. ..cc

The process is begun by dissolving the resin in 60 cc. of Water in the presence of 2-amino-2-methyl-1-propanol to a final pH of 8.2. The tetrasodium salt of ethylene diamine tetracetic acid is added to serve as a sequestrant for metals, followed by the mixture of ethyl alcohol and perfume. The volume is increased to 100 cc. by adding distilled water and the pH adjusted to 8.5 by adding more 2-amino-2-methyl-1-propanol.

20 cc. of the solution obtained in this manner is applied to hair which has been washed and dried, taking care to distribute the solution uniformly. The hair is then set in a conventional manner. Hair treated in this way is bright, soft, silky, vibrant and easily put up.

The lotion which has just been described remarkably prolongs the life of the wave without causing the hair to become dull, even in very humid weather.

Example 21 In accordance with the invention, a setting lotion having the following composition is prepared:

The condensation product of B-mercapto-ethylamine and N,N-diethy1propylene-diamine on the methyl methacrylate/maleic anhydride copolymer ob- Tetrasodium salt of ethylene diamine tetracetic acid g Water, q.s.p cc

13 When used as in Example 20, equally good results are obtained.

Example 22 In accordance with the invention an aerosol foam for projection from a bomb to use in setting the hair is prepared from the following constituents:

Condensation product of the acrylonitrile/maleic anhydride copolymer with 1(B-amino-ethyl) thioglycolamide and n-butylamine, obtained as in Ex- The aerosol bomb is made by first dissolving the resin in 30 cc. of water in the presence of 2-amino-2-methyl-1- propanol. Cetyl stearyl alcohol which has been dissolved in 20 cc. of water, while heating it slightly, is then added, after which the mixture of ethyl alcohol and perfume is added.

The pH is then brought to 8.5 by adding the necessary quantity of 2-amino-2-methyl-l-propanol and the volume increased to 93 g. by adding distilled water.

The aerosol bomb is pressurized by adding 7 g. of a conventional propellant such as the fluorinated hydro carbon sold under the trade name Freon 12.

The product is applied as a very transient foam, thus facilitating its distribution through the previously washed and dried hair.

The hair is then set in a conventional manner, with excellent results.

What is claimed is:

1. a polymer that is soluble in aqueous solutions, comprising repeating monomer units having the following formula:

in which:

R and R" are both selected from the group consisting of hydrogen, lower alkyl, phenyl, and lower alkoxy, R is selected from the group consisting of OCOCH COOCH and -CEN, Q is a radical having the following formula:

R is selected from the group consisting of H and CH R is selected from the group consisting of H and COOH,

q is a whole number between 1 and 5, inclusive,

q is an integer from to 1 inclusive,

p is an integer from 0 to 1 inclusive,

14 Q is a radical having the formula:

a -1 T--(CHg) CH2CH2-R4 in which:

R, is selected from the group consisting of hydrogen,

and lower alkyl,

R is selected from the group consisting of a lower alkyl and a radical having the formula in which 1 is selected from the group consisting of lower alkyl amines and a heterocyclic ring,

m is a whole number lying between 2 and 4, inclusive.

2. A polymer as claimed in claim 1 in which the substituents Q and Q constitute from 20 to of the total polymer.

3. A polymer as claimed in claim 1 which is watersoluble at an alkaline pH.

4. A polymer as claimed in claim 1 in which both -R' and R" are hydrogen atoms and R' is the radical OCOCH 5. A polymer as claimed in claim 1 in which both R and R" are hydrogen atoms and R' represents the radical -CEN.

6. A polymer as claimed in claim 1 in which both R and R" are hydrogen atoms and R' is the radical COOCH 7. A polymer as claimed in Claim 1 in which R is a hydrogen atom, R is the CH radical, and R' represents the COOCH radical.

8. The polymer claimed in claim 1 in which Q is B- mercaptoethylamine.

9. The polymer claimed in claim 1 in which Q is cysteine.

10. The polymer claimed in claim 1 in which Q is N- mono methyl mercaptoethylamine.

11. The polymer claimed in claim 1 in which Q is N- (fl-aminoethyl thioglycolamide.

12. The polymer claimed in claim 1 in which Q is butylamine.

13. The polymer claimed in claim 1 in which Q is N,N-diethyl-propylenediamine.

14. The polymer claimed in claim 1 in which Q is N-(p-aminoethyhmorpholine.

References Cited UNITED STATES PATENTS 2,313,565 3/1943 McDowell et al. 26078 2,977,334 3/1961 Zopf et al. 260--27 JOSEPH L. SCHOFER, Primary Examiner C. A. HENDERSON, J R., Assistant Examiner U.S. C1. X.R. 260-78; 42447, 72 

